Process fok



April zo, 1954 2,676,141

PROCESS FOR. REMOVING WAX AND OTHER IMPURITIES FROM OIL V, H. KANE ETAL Filed June 30, 1950 Patented Apr. 20, i954 rnoosss ros nEMoviNo WAX AND orner, nvironrrms FROM on.

Vernon H. Kane and George R. Belli/ille, Jr., Port Arthur, Tex., assignors to The Texas Company, New York, N. Y., a -corporation of Delaware Application .i une 39,1950, Serial No. 171,468

(Gl. 19t-17) 6 Claims.

This invention relates to a process for removing Wax constituents and other undesirable matter from an oil, such as mineral oil. More particularly, it involves a process for treating an oil with an organic compound which forms crystal complexes with various types of hydrocarbon materials. Examples of the complex-forming organic compounds which are used in the process of this invention are urea and thiourea.

This application is a continuation-in-part of our co-pending application, Serial No. 84,065, filed March 29, 1949, wherein there is disclosed a process for effecting complex formation by contacting an organic mixture containing complexforming compounds with a Contact massy comprising complexing agent and a solid supporting material which can be either an adsorbent compound or a non-adsorbent granular solid. In the parent application it is disclosed that the composite contacting mass comprising complex-y ing agent and supporting material can be employed either in a stationary bed or in afslurrytype system. This invention involves the discovery that when complex formation is effected by contact of organic mixture with a stationary bed of composite contacting agent, there is a critical concentration oi complexing agent in the contact mass. Unless the contact mass contains the prescribed critical proportions of complexing agent and supporting material, successful operation is not realized.

In accordance with the process of this invention, organic mixtures containing compounds that form complexes with complexing agents of the urea type are contacted with a stationary bed of a composite contact mass comprising 5 to 35 per cent complexing agent and 65 to 95 per cent supporting carrier. On passage of the organic mixture containing complex-forming compounds through the stationary contact mass of the prescribed composition, complex forma for the complex formation and are indeed recom-y mended in certain modifications thereof,r normally temperatures between 70 and 150 F. are

employed. When complex formation is effected by passage of an orga'inicv mixture through a composite contact mass of the prescribed composition, removal of 'complex-forming constituents from an orga-'nic mixture is readily accomplished by a simple process which is free from operational diiiiculties.

The process oi the invention is particularly applicable to the removal of waxy components from a VWax-bearingoil to produce Wax-free product. In such processes advantage is taken or" the specificity of urea in complex Aformation. Urea forms complexes with normal aliphatic hydrocarbons containing `four or morev carbon atoms. Reduced temperatures are'required for the formation offurea complexes with C4 to Cs f hydrocarbons, Whereascomplex formation occurs at atmospheric temperatures with normalhydro-Y carbons containing r`ten or more carbon atoms. Some terminally-substituted vnormal hydrocarbons such asnormalY decanol and l-chloro-dodeca-ne also form complexes With urea. Normal paraii'in waxes are readily removed by the process of this invention Yfrom gas oil fractions to produce 10W pour diesel oils which are in demand for cold'vveather operation of diesel engines and from 10W Wax content lubricating oil stocks to produce turbine oils, refrigerator oils and hydraulic oils characterized by very low pourI and Freon haze test. In further description of the process of this invention, the complex-forming reaction of urea with normal parains Will be used to illustrate the invention.

The formation of complexesbetween normal aliphatic compounds and urea is facilitated by the presence or" at least a small quantity of a liquid having mutual solubility for the complex.- forming agent and hydrocarbons. Water and low molecular Weight oxygenated Lcom-pounds are effective in expediting complex formation; alcohols suchcas methyl, propyl and butyl alcohols, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone are examples Aof oxygenates that promote complex formation. Apparently these solvents facilitate complex formation by acting as a medium for molecular con ltact between urea and the normal hydrocarbons. In the process of this invention the carrier portion of the compositecontact ,mass acts as a reservoir for the polar solvent so vthat complex formation between organic complexing `agent and waxy components of a feed oil is promoted by the presence of relatively small quantities of polar compound. Wetting the bed with polar solvent prior to introduction of the feed oil into the contact zone provides sufficient complex-pro-I mation throughout the whole period of contact.

3 The carrier portion of the composite contact mass is advantageously a solid adsorptive material which may be either a synthetic adsorbent or a naturally occurring earth or clay; silica gel, fullers earth, and bauxite are examples of adsorbents that are particularly useful in the process of this invention. Non-adsorbent granular solids, such as sand, may also be employed but their use is not recommended. The use of an adsorbent carrier is particularly advantageous because a substantial measure of refining is effected in addition to wax removal. When the composite contact mass comprises urea and an adsorbent carrier such as Porocel in the prescribed quantities, there is effected not only substantialv improvein the pour point and haze test of the resulting oil, but there is also realized a substantial color improvement. Accordingly, in the preferred modication of this invention the composite contact mass comprises 5 to 35 per cent urea and 65 to 95 per cent solid adsorbent particles. When non-adsorbent supporting materials such as sand, kieselguhr, etc. are employed, only dewaxing of the oil stock is eifected and there is no accompanying refining of the oil fraction. V

. The contact mass advantageously contains 15 to 30 per cent complexing agent and 70 to 85 per cent carrier. Ordinarily complex formation is eifected with a contact mass having a composition within this preferred range. An especially preferred contact mass contains approximately 25 per cent urea and 75 per cent Porocel.

Contact of the oil with the composite contact mass is effected at temperatures above the pour point of the oil to temperatures of 180 F., at which temperature substantial decomposition of the complex occurs. eifected at temperatures between 70 and 125 F. The process of the invention is illustrated by subjecting a turbine oil to contact with a stationary bed of composite contact mass comprising 25 per cent urea and '75 per cent of 15 mesh Porocel. The feed turbine oil is characterized by the following tests:

Gravity, API 23.7 Flash, COC, F 385 Fire, COC, F 440 Viscosity, SSU at 100 F 305 Viscosity, SSU at 130 F 133 Color. 6" Lovi 85 Pour, EL -25 Corr. Cu strip at 212 F Neg. Neut. No 0.02 Sap. No 0.06 Ash, per cent None Emulsion at 130 F.: Y

Distilled water 40-40-0-30 Salt water (1%) 40-40-0-30 N/l caustic solution 40-40-0-30 Demulsibility at 130 F 900 Dielectric strength, volts 25,800 Freon wax precipitation test1:

Haze, F Above -22- Floc, F Above -22 1 This test consists of mixing nine cc. of Frech-12 with one cc. of oil to be tested, chilling the mixture at the rate of 1 to 2 F./min. and observing the temperatures at which Wax is rst observed (haze temperature) and the temperature at which large agglomerates of wax form (fioc temperature).

In the accompanying figure there is illustrated the processing steps to which the feed turbine oil is subjected in order to yield a finished product of low Freon haze test and improved color characteristics, which is an excellent refrigerator ,011.1

Ordinarily the contact is A lter vessel 2 is filled with about 35 to 60 tons of filter medium comprising a contact mass consisting oi 25 weight per cent urea and '75 weight per cent Porocel. A preferred manner of preparation involves carrying adsorbent on conveyor 40 and mixing a predetermined quantity of urea delivered in particle form from storage hopper 38 by conveyor 39. This mixture containing the prescribed concentration of urea and adsorbent is then charged to the lter 2.

The bed is then saturated with a saturated solution of urea in methyl alcohol at about F. delivered from storage vessel 4l by pipe d2.

A stream of the charge oil is conducted from a source not shown through pipe l at a temperature of about 100 F. and introduced either to the top of lter vessel 2 or alternately through pipe la to the bottom of the filter vessel 2. Antigravity Vflow is preferred because the rate of flow is more easily controlled in this type of operation.

The feed oil stream is introduced at a rate of about 1.0 to 2.0 barrels of oil per ton of adsorptive medium per day and allowed to iiow or is pumped through the lter bed. During passage through the filter bed the clay exerts a decolorat'which point the iiow of fresh feed oil is dis- Y continued to permit recovery of the chemicalsl in the spent filter bed and regeneration of the Contact mass, as described later. Employing a contact mass of the prescribed composition, the complexing ability of the filter bed is exhausted prior to clogging of the unit due to complex formation.

During the period of processing iiow, the treated oil is discharged from the lter through a pipe 3 or 3a, at the top or bottom of the filter,

depending on whether gravity or anti-gravity flow is employed, into a tower 5 wherein any solvent or urea, picked up by the oil in its passage through the contact mass, is removed by solution in a countercurrent stream of water orv other solvent introduced through pipe 6 into a zone at the opposite end of the tower. The oil is removed from the tower through pipe intoA either a vacuum dehydrator Il by way of pipe 8 or through a conventional blotter press l2 by way of pipe IB, to eiect a iinal drying by removing residual traces of solvent. Finished oil is discharged from the system through pipe I3.

Alternately, depending upon the solvent and urea content of the dewaxed oil, the dewaxed oil may be conducted through pipes 3 or 3a, 4 and 6I directly into vacuum dehydrator vessel Il where steam may optionally be introduced through line I1 to effect removal of solvent overhead through pipe !5. The oil from the vacuum dehydrator in this scheme of operation is conducted through pipes IB and It into blotter press i2 to effect removal of solid urea which may be present in the oil, as well as any residual moisture whichV may remain after the dehydration operation, or it may be removed from the dehydrator through pipes I0, 62 and I3 as finished oil.

The eiiiuent water from tower 5 is drawn 01T through pipe i4 to reject, or the minor amounts lof solvent, less than about 0.5 per cent by weight of the water, and ureaflless than about 0.2 per cent by weight cf thewater, may-.bc recovered by any suitabley methods.

Gravity, API 23.2 FlaSh, COC, F r375 Fire, COC, F 425 Viscosity, SSU at 100 F 311 Viscosity, SSU at 130 F 135 Color, 6 Lovi 60 Pour, F a5 Corr. Cu strip at 212 F Neg. Neut. No .02Vv Sap.`l\lo1 .06 Ash, per cent None Emulsion at 130 F.: Y

Distilled water 4040--15 Salt Water (1%) v40--40-0-15 N /l caustic 490-40-0-15 Deniulsibility at 130 F 162,0 Bieleotric'strength, volts 31,300 Fre on 'wax precipitation test:

Haze, F 65 Floc, F. below -80 It is apparent that Freon haze test of the treated oil is substantially improved over that of the feed oil; the treated oil which has a haze test of 65 F. is an excellent refrigerator oil. It will also be noted that a 25 unit improvement in Lovibond color is effected by treatment in accordance with the process of the invention.

If the composite contact mass contained more than 35 per cent urea, plugging of the contactor wbuld have resulted within a short period after initial contact. If less than 5 per cent urea were present in the composite contact mass, substantially no removal of complex-forming constituents would be effected. it is apparent then that it is necessary to maintain the composition of the contact mass within the specified critical ranges in order to have a feasible operation.

Regeneration of the composite contact mass is effected by means which are disclosed in the co-pending aforementioned parent application. The complex may be removed from the bed by passing a hot hydrocarbon solvent at a temperature of 125 to 250 F. therethrough or by means of water at a temperature above 190 F. The hydrocarbon solvent decomposes the complex and removes the normal paraflins therefrom in solution. The hot water solution decomposes the complex and dissolves urea with the resulting formation of a 2-phase system in which the upper layer is predominantly paraimic waxes and the lower layer is aqueous urea solution. After removal of complex and urea from the bed, the adsorbent can be regenerated by burning with air at a temperature of 9.00 to 1100 F. After regeneration of the adsorbent by burning, urea which has been isolated from the aqueous solution obtained on decomposition of the complex can be recombined with the adsorbent in the prescribed proportions to form a reactive composite contact mass.

Various means are available for wetting the composito .oo niaot with colar .solyent indicatori previously, the wot prior .tot o oharso of. the hydrocarbon 5011.1: iionby Pe. Iig a S. .al- 1 vquar-1tty of .oxyso hvorooarbo therethrough! A preferred met sl AWo'wire-of. the lood involves. pas. ng, solution of Solvent .through the.

bod'jof contact mtos vprior to yintroduction :of the d alternative paralilio constituents of Vthe charge.

Oils which have been oontaoted .with urcaapf., pear Ato lhave `superior oxidation characteristicsto those o fjoil contacted `with .clay alone. Refriger- 3120.1 ,QllQlotainedby-the process of this invention appears lto have foaming characteristics,superior to those of oil which has no tbecn contacted `with.

urea. f v- The Waller-.Separating characteristics nof .,lubri: caries, oil Stools are. improves by than ferrea process of this inventionwhich is separating resins and oxygenated mate the 'f eedoil. v

Also. c is. 'contemplates' that ne? processie application to treatment for other, tyres 'or ons than m05@ Spaul' melitolled lflufllg Q ...S derived from 'animal' vegetable and marine sources, as well as those produced by synthetic means.

When the process of the invention is employed in the treatment of relatively viscous lubricating oil stocks in commercial size filters, it is advantageous to dilute the feed oil with a light hydrocarbon fraction. Apparently high viscosity oils tend to channel through the contact mass so that incomplete complex formation occurs between the urea of the contact mass and the normal parainic constituents of the viscous oil. This difficulty is simply obvated by reducing the viscosity of the oil stock by the addition of a diluent hydrocarbon fraction. In general, the viscosity of lubricating oil should be reduced below 100 Saybolt Universal visc. at 100 F. prior to its treatment in the process of the invention. For example, a lubricating oil stock having a Saybolt Universal visc. of 300 at 100 F. is cut back with 15 per cent naphtha to give the diluent mixture a Saybolt Universal visc. of the diluted mixture is readily dewaxed in accordance with the process of this invention, whereas the heavy undiluted oil can not be dewaxed readily in commercial size filters.

It will be understood that in practice a plurality of lter vessels may be employed so that when one vessel is off-stream for reactivation, the feed stream of oil can be diverted to another vessel used for the same purpose.

Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and, therefore, only such limitations should be imposed as are indicated in the appended claims.

We claim:

l. In a process for separating complex-forming hydrocarbons which are predominantly normally aliphatic in nature from a hydrocarbon mixture by contact with urea, the steps which comprise disposing within a. contacting zone a contact mass comprising 5 to 35 per cent urea and 65 to 95'per cent solid adsorbent, passing said hydrocarbon mixture inthe liquid phase in contact with said mass in the presence of at least a small amount of polar solvent having mutual solubility for urea and hydrocarbons and selected from the group consisting of water and oxygenated hydrocarbons, e'ecting said contact at a temperature up to 180 F. whereby the complex-forming hydrocarbon constitutents of said hydrocarbon mixture enter into complex formation with said urea, and discharging from said contact zone a hydrocarbon mixture from which complex-forming hydrocarbon constituents have been removed.

2. A process according to claim 1 in which the solid adsorbent is selected from the group consisting of synthetic adsorbents and naturally occurring clays and earths.

3. A process according to claim 1 in which the hydrocarbon mixture is a wax-bearing oil.

4. A process according to claim 1 in which the contact mass comprises 15 to 30 per cent urea and 70 to 85 per cent solid adsorbent.

5. In a process for separating waxy constituents from a viscous wax-bearing oil by contact with urea, the steps which comprise disposing within a contacting zone a contact mass comprising 5 to 35 per cent urea and 65 to 95 per cent solid adsorbent, diluting said wax-bearing oil with a light hydrocarbon fraction, passing said diluted wax-bearing oil in the liquid phase in contact with said mass in the presence of at least a small References Cited in the 111e of this patent UNITED STATES PATENTS Number Name Date 1,278,023 Rosenbaum Sept. 3, 1918 1,509,325 Weir et al Sept. 23, 1924 1,830,859 Schotte Nov. 10, 1931 2,381,293 La Lande Aug. 7, 1945 2,386,354 Schulze et al Oct. 9, 1945 2,499,820 Fetterly Mar. '7, 1950 2,520,716 Fetterly Aug. 29, 1950 2,546,328 Arabian et al Mar. 27, 1951 2,560,193 Shoemaker July 10, 1951 OTHER REFERENCES Technical Oil Mission, Reel 143, translation by Shell Development Co. of German application B 190,197 (Bengen) deposited in Library of Congress, May 22, 1946; included in Index released May 31, 1946 5 pages, pages 2-6 inclusive only). 

1. IN A PROCESS FOR SEPARATING COMPLEX-FORMING HYDROCARBONS WHICH ARE PREDOMINANTLY NORMALLY ALIPHATIC IN NATURE FROM A HYDROCARBON MIXTURE BY CONTACT WITH UREA, THE STEPS WHICH COMPRISE DISPOSING WITHIN A CONTACTING ZONE A CONTACT MASS COMPRISING 5 TO 35 PER CENT UREA AND 65 TO 95 PER CENT SOLID ADSORBENT, PASSING SAID HYDROCARBON MIXTURE IN THE LIQUID PHASE IN CONTACT WITH SAID MASS IN THE PRESENCE OF AT LEAST A SMALL AMOUNT OF POLAR SOLVENT HAVING MUTUAL SOLUBILITY FOR UREA AND HYDROCARBONS AND SELECTED FROM THE GROUP CONSISTING OF WATER AND OXYGENATED HYDROCARBONS, EFFECTING SAID CONTACT AT A TEMPERATURE UP TO 180* F. WHEREBY THE COMPLEX-FORMING HYDROCARBON CONSTITUENTS OF SAID HYDROCARBON MIX- 